AU777654B2 - Long life medium and high ash oils with enhanced nitration resistance - Google Patents
Long life medium and high ash oils with enhanced nitration resistance Download PDFInfo
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- AU777654B2 AU777654B2 AU20912/01A AU2091201A AU777654B2 AU 777654 B2 AU777654 B2 AU 777654B2 AU 20912/01 A AU20912/01 A AU 20912/01A AU 2091201 A AU2091201 A AU 2091201A AU 777654 B2 AU777654 B2 AU 777654B2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Carbon And Carbon Compounds (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Glanulating (AREA)
Abstract
A long life lubricating oil as evidenced by a reduction in viscosity increase, oxidation and nitration, comprises a major amount of a base oil of lubricating viscosity and a minor amount of a mixture of high TBN, medium TBN and low/neutral TBN detergents wherein metal salicylate detergent is at least one of the medium or low/neutral TBN detergents.
Description
WO 01/44418 PCT/US00/33683 I -I- LONG LIFE MEDIUM AND HIGH ASH OILS WITH ENHANCED NITRATION RESISTANCE FIELD OF THE INVENTION The present invention relates to medium and high ash engine oils of extended life as evidenced by a reduction in viscosity increase, oxidation and nitration, comprising a base oil of lubricating viscosity and a particular combination of detergents.
BACKGROUND OF THE INVENTION Natural gas fired engines are large, having up to 16 cylinders, and often generating between 500-3000 HP. The engines are typically used in the Oil and Gas industry to compress natural gas ai well heads and along pipelines.
Due to the nature of this application, the engines often run continuously near full load conditions, shutting down only for maintenance such as for oil changes.
This condition of running continuously near full load places severe demands on the lubricant. Indeed, since the lubricant is subjected to a high temperature environment, the life of the lubricant is often limited by oil oxidation processes.
Additionally, since natural gas fired engines run with high emissions of oxides of nitrogen (NOx), the lubricant life may also be limited by oil nitration processes. Therefore, it is desirable for gas engine oils to have long life through enhanced resistance to oil oxidation and nitration.
The combustion of diesel fuel often results in a small amount of incomplete combustion exhaust particulates). The incombustibles provide a small but critical degree of lubrication to the exhaust valve/seat interface, thereby ensuring the durability of both cylinder heads and valves. The combustion of natural gas is often very complete, with virtually no incombustible WO 01/44418 PCT/US00/33683 -2materials. Therefore, the durability of the cylinder head and valve is controlled by the properties of the lubricant and its consumption rate. For this reason, gas engine oils are classified according to their ash content, since it is the lubricant ash which acts as a solid lubricant to protect the valve/seat interface. The oil industry has accepted guidelines which classify gas engine oils according to their ash level. The classifications are: Ash Designation Ash Level (wt/o, ASTM D874) Ashless Ash 0.1% Low Ash 0.1 Ash 0.6 Medium Ash 0.6 Ash High Ash Ash The ash level of the lubricant is often determined by its formulation componieits, with metal-containing detergents barum, calcium) and metallic-containing antiwear additives contributing to the ash level of the lubricant. For correct engine operation, gas engine manufacturers define lubricant ash requirements as part of the lubricant specifications. For example, manufacturers of 2-cycle engines often require the gas engine oil to be Ashless in order to minimize the extent of harmful deposits which form on the piston and combustion chamber area. Manufacturers of 4-cycle engines often require the gas engine oils to be Low, Medium or High Ash to provide the correct balance of engine cleanliness, and durability of the cylinder head and valves. Running the engine with too low an ash level will likely result in shortened life for the valves or cylinder head. Running the engine with too high an ash level will likely cause excessive deposits in the combustion chamber and upper piston area.
Gas engine oil of enhanced life as evidenced by an increase in the resistance of the oil to oxidation, nitration and deposit formation is the subject of US Patent Number 5,726,133. The gas engine oil of that patent is a low ash gas engine oil comprising a major amount of a base oil of lubricating viscosity and a minor amount of an additive mixture comprising a mixture of detergents comprising at least one alkali or alkaline earth metal salt having a Total Base Number (TBN) of about 250 and less and a second alkali or alkaline earth metal salt having a TBN lower than the aforesaid component. The TBN of this second alkali or alkaline earth metal salt will typically be about half or less that of the aforesaid component.
The fully formulated gas engine oil of US Patent Number 5,726,133 can also typically contain other standard additives known to those skilled in the art, including dispersants (about 0.5 to 8 vol%), phenolic or aminic anti-oxidants (about 0.05 to 1.5 vol%), metal deactivators such as triazoles, alkyl substituted dimercaptothiadiazoles (about 0.01 to 0.2 vol%), anti wear additives such as metal di thiophosphates, metal dithiocarbamates, metal xanthates or tricresylphosphates (about 0.05 to 1.5 vol%), pour point depressants such as poly (meth) acrylates or alkyl aromatic polymers (about 0.05-0.6 vol%), anti foamants such as silicone antifoaming agents (about 0.005 to 0.15 vol%), and viscosity index improvers, such as olefin copolymers, polymethacrylates, styrenediene block copolymers, and star copolymers (up to about 15 vol%, preferably up 20 to about10 vol%).
SUMMARY OF THE INVENTION The present invention relates to a lubricating oil of extended life as evidenced by reductions in viscosity increase, oxidation and nitration, relative to current commercial and reference oils, which comprises a major amount of a base oil of lubricating viscosity and a minor amount of a mixture of metal °m 0 salicylate detergent(s) and a metal sulfonate and/or metal phenate detergent(s).
WO 01/44418 PCT/US00/33683 -4- The present lubricating oil would be particularly useful as a medium ash or high ash gas engine oil.
DETAILED DESCRIPTION OF THE INVENTION A lubricating oil composition is described comprising a major amount of a base oil of lubricating viscosity and a minor amount of a mixture of one or more metal salicylate detergent(s), and one or more metal phenate(s) and/or metal sulfonate detergents. Also described is a method for extending the life of lubricating oils as evidenced by a reduction in viscosity increase, oxidation and nitration by adding to the oil an additive comprising a mixture of one or more metal salicylate detergent(s), and one or more metal sulfonate(s) and/or one or more metal phenate(s).
The lubricating oil base stock is any natural or synthetic lubricating base oil stock fraction typically having a kinematic viscosity at 100 0 C of about to 20 cSt, more preferably about 7 to 16 cSt, most preferably about 9 to 13 cSt.
In a preferred embodiment, the use of the viscosity index improver permits the omission of oil of viscosity about 20 cSt or more at 100°C from the lube base oil fraction used to make the present formulation. Therefore, a preferred base oil is one which contains little, if any, heavy fraction; little, if any, lube oil fraction of viscosity 20 cSt or higher at 100 0
C.
The lubricating oil basestock can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating oil basestocks include basestocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate basestocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
WO 01/44418 PCT/US00/33683 Suitable basestocks include those in API categories I, II and III, where saturates level and Viscosity Index are: Group I less than 90% and 80-120, respectively; Group II greater than 90% and 80-120, respectively; and Group III greater than 90% and greater than 120, respectively.
Natural lubricating oils include animal oils, vegetable oils rapeseed oils, castor oils and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and inter-polymerized olefms, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogues and homoiogues thereof, and the like. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with variety of alcohols. Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers. Trialkyl phosphate ester oils such as those exemplified by tri-n-butyl phosphate and tri-iso-butyl phosphate are also suitable for use as base oils.
Silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
WO 01/44418 PCT/US00/33683 -6- The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source coal, shale, or tar sand bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
The resulting isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions of specific viscosity WO 01/44418 PCT/US00/33683 -7range. Wax isomerate is also characterized by possessing very high viscosity indices, generally having a VI of at least 130, preferably at least 135 and higher and following dewaxing, a pour point of about -20 0 C and lower.
The production of wax isomerate oil meeting the requirements of the present invention is disclosed and claimed in U.S. Patent Nos. 5,049,299 and 5,158,671.
The detergent is a mixture of one or more metal salicylate detergents with one or more metal sulfonates and/or one or more metal phenates. The metals are any alkali or alkaline earth metals, calcium, barium, sodium, lithium, potassium, magnesium, more preferably calcium, barium and magnesium. It is a feature of the present lubricating oil that each of the metal salts or r-ouins of metal salts used in the mixture has a different TBN as compared with the other metal salts or groups of metal salts in the mixture.
Thus, the mixture of detergents comprises a first metal salt or group of metal salts selected from the group consisting of one or more metal sulfonate(s), salicylate(s), phenate(s) and mixtures thereof having a high TBN of greater than about 150 to 300 or higher, preferably about 160 to 300, used in an amount in combination with the other metal salts or groups of metal salts (recited below) sufficient to achieve a lubricating oil of at least 0.65 wt%/ sulfated ash content, a second metal salt or group of metal salts selected from the group consisting of one or more metal salicylate(s), metal sulfonate(s), metal phenate(s) and mixtures thereof having a medium TBN of greater than about to 150, preferably about 60 to 120, and a third metal salt or group of metal salts selected from the group consisting of one or more metal sulfonate(s), metal salicylate(s) and mixtures thereof identified as neutral or low TBN, having a TBN of about 10 to 50, preferably about 20 to 40, the total amount of medium plus (neutral) low TBN detergent being about 0.7 vol% or higher (active ingredient), preferably about 0.9 vol% or higher (active ingredient), most preferably about 1 vol% or higher (active ingredient), wherein at least one of the medium or low/neutral TBN detergent(s) is metal salicylate, preferably at least one of the medium TBN detergent(s) is a metal salicylate. The total amount of high TBN detergents is about 0.3 vol% or higher (active ingredient), preferably about 0.4 vol% or higher (active ingredient), most preferably about 0.5 vol% or higher (active ingredient). The mixture contains salts of at least two different types, with medium or neutral salicylate being an essential component. The volume ratio (based on active ingredient) of the high TBN detergent to medium plus neutral/low TBN detergent is in the range of about 0.15 to 3.5, preferably 0.2 to 2, most preferably about 0.25 to 1.
The mixture of detergents is added to the lubricating oil formulation in an amount up to about 10 vol% based on active ingredient in the detergent mixture.
preferably in an amount up to about 8 vol% based on active ingredient, more preferably up to about 6 vol% based on active ingredient in the detergent mixture, most preferably between about 1.5 to 5.0 vol%, based on active ingredient in the detergent mixture. Preferably, the total amount of metal salicylate(s) used of all TBN's is in the range of between about 0.5 vol% to 4.5 vol%, based on active 20 ingredient of metal salicylate.
The formulation may also contain one or more of the commonly used additives. Thus, in addition to the recited detergents, the oil composition can contain one or more antioxidants (phenolic, aminic or other), viscosity index improvers, pour point depressants, antiwear/extreme pressure additives, antifoamant, dyes, metal deactivators, etc.
WO 01/44418 PCTIUS00/33683 -9- Anti-oxidants useful in the present invention may be of the phenol o,o' ditertiary alkyl phenol such as ditertiarybutyl phenol), or amine dialkyl diphenylamine such as dibutyl, octylbutyl or dioctyl diphenylamine) type, or mixtures thereof. These should be substantially non-volatile at peak engine operating temperatures. By substantially non-volatile is meant that there is less than 10% volatility at about 150 0 C, preferably at about 175 0 C, most preferably at about 200 0 C and higher. The term "phenol type" used herein includes compounds having one or more than one hydroxy group bound to an aromatic ring which may itself be mononuclear, benzyl, or polynuclear, naphthyl and spiro aromatic compounds. Thus "phenol type" includes phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurized alkyl or alkenyl derivatives thereof, and bisphenol type compounds including such bi-phenol compounds linked by alkylene bridges or sulfur or oxygen bridges. Alkyi phenols include mono- and poly-alkyl or alkenyl phenols, the alkyl or alkenyl group containing from about 3-100 carbons, preferably 4 to 50 carbons and sulfurized derivatives thereof, the number of alkyl or alkenyl groups present in the aromatic ring ranging from 1 to up to the available unsatisfied valences of the aromatic ring remaining after counting the number of hydroxyl groups bound to the aromatic ring.
Generally, therefore, the "phenolic type" anti-oxidant may be represented by the general formula: (R)x Ar (OH)y (R')q where Ar is selected from the group consisting of: 0- 0 (CH2)z Q (CH 2 (S)z (Ch2)n- \CH4-m (R")p wherein R is a C 3 -CioO alkyl or alkenyl group, a sulfur substituted alkyl or alkenyl group, preferably a C 4
-C
5 0 alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably C 3
-C
10 0 alkyl or sulfur substituted alkyl group, most preferably a C 4
-C
5 0 alkyl group, y ranges from I to up to the available valences of Ar, x ranges from 0 to up to the available valances of Ar-y, Q ranges from 0 to up to the available valences ofAr+(x y z ranges from I to 10, n ranges from 0 to 20, and m is 0 to 4 and P is 0 or 1, preferably y ranges from I to 3, x ranges from 0 to 3, z ranges from 1 to 4 and n ranges from 0 to p is0 and Q is 0 or 1.
Most preferably the phenol is a hindered phenol such as di isopropyl phenol, di-tert butyl phenol, di tert butyl alkylated phenol where the alkyl 11 substitutent is hydrocarbyl and contains between 1 and 20 carbon atoms, such as 2,6 di-tert butyl-4 methyl phenol, 2,6-di-tert butyl-4-ethyl phenol, etc., or 2,6 di-tert butyl-4-alkoxy phenol.
Phenolic type anti-oxidants are well known in the lubricating industry and to those skilled in the art. The above is presented only by way of exemplification, not limitation on the type of phenolic anti-oxidants which can be used in the present invention.
The amine type antioxidants include diarylamines and thiodiaryl amines.
Suitable diarylamines include diphenyl amine; phenyl-a-naphthylamine; phenyl-p-naphthylamine; a-a-di-naphthylamine; P--dinaphthylamine; or a-p-dinaphthylamine. Also suitable antioxidants are diarylamines wherein one or both of the aryl groups are alkylated, e. with linear or branched alkyl groups containing 1 to 12 carbon atoms, such as the diethyl diphenylamine; dioctyldiphenyl amines, methyl phenyl-a-naphthylamines phenyl-B-(butylnaphthyl) amine; di (4-methyl phenyl) amine or phenyl (3-propylphenyl) amine octyl-butyl-diphenylamine, dioctyldiphenyl amine, octyl-, nonyl-diphenyl amine, dinonyl di phenyl amine and mixtures thereof.
Suitable thiodiarylamines include phenothiazine, the alkylated phenothiazines, phenyl thio-a-naphthyl amine; phenyl thio-p-naphthylamine; 20 a-a-thio dinaphthylamine; p-p-thio dinaphthylamine; phenyl thio-a (methyl naphthyl) amine; thio-di (ethyl phenyl) amine; (butyl phenyl) thio phenyl amine.
Other suitable antioxidants include s-triazines of the formula *e *o* *o o *~o WO 01/44418 PCT/US00/33683 -12- N
R
R
7
N
R
N N
N
R 10 \R 1 Rio R wherein R 8
R
9
R
I
o, are hydrogen, C 1 to C 2 0 hydrocarbyl or pyridyl, and R 7 is C 1 to C 8 hydrocarbyl,
C
1 to C 2 0 hydrocarbylamine, pyridyl or pyridylamine.
If desired, mixtures of antioxidants may be present in the lubricant composition of the invention. The total amount of antioxidant or antioxidant mixtures used rana e from ahout 0 0 to 20 vol%/, preferably about 0.1 to 1.75 vol%, most preferably about 0.5 to 1.5 vol%.
Viscosity index improvers useful in the present invention include any of the polymers which impart enhanced viscosity properties to the finished oil and are generally hydrocarbon-based polymers having a molecular weight, Mw, in the range of between about 2,000 to 1,000,000, preferably about 50,000 to 200,000. Viscosity index improver polymers typically include olefin copolymers, ethylene-propylene copolymers, ethylene-(iso-) butylene copolymers, propylene-(iso-)butylene copolymers, ethylene-poly alpha olefm copolymers, polymethocrylates; styrene-diene block copolymers, styrene-isoprene copolymers, and star copolymers. Viscosity index improvers may be monofunctional or multifunctional, such as those bearing substitutents that provide a secondary lubricant performance feature such as dispersancy, pour point depression, etc.
WO 01/44418 PCT/US00/33683 13 Viscosity index improvers are lubricant additives well known in the lubricant industry and to those skilled in the art. The above is presented only by way of example and not as a limitation on the types of viscosity index improvers which can be used in the present invention.
The amount of viscosity index improver used, be it mono functional or multifunctional, is in the amount of about 0.1 to 3 vol%, preferably about 0.2 to 2 vol%, most preferably about 0.3 to 1.5 vol%.
The fully formulated lubricating oil may contain other additional, typical additives known to those skilled in the industry, used on an as-received basis.
I IiTh, the fuiuy formuld ol umaiy lntain dispersants of the ty generally represented by succinimides polyisobutylene succinic acid/anhydride (PIBSA)-polyamine having a PIBSA molecular weight of about 700 to 2500). The dispersants may be borated or non-borated. The dispersant can be present in the amount of about 0.5 to 8 vol%, more preferably in the amount of about 1 to 6 vol%, most preferably in the amount of about 2 to 4 vol%.
Metal deactivators may be of the aryl thiazines, triazoles, or alkyl substituted dimercapto thiadiazoles (DMTD's), or mixtures thereof. Metal deactivators can be present in the amount of about 0.01 to 0.2 vol%, more preferably in the amount of about 0.02 to 0.15 vol%, most preferably in the amount of about 0.05 to 0. 1 vol%.
Antiwear additives such as metal dithiophosphates zinc dialkyl dithiophosphate, ZDDP), metal dithiocarbamates, metal xanthates or tricresyl- 14 phosphates may be included. Antiwear additives can be present in the amount of about 0.05 to 1.5 vol%, more preferably in the amount of about 0.1 to vol%, most preferably in the amount of about 0.2 to 0.5 vol%.
Pour point depressants such as poly (meth) acrylates, or alkylaromatic polymers may be included. Pour point depressants can be present in the amount of about 0.05 to 0.6 vol%, more preferably in the amount of about 0.1 to 0.4 vol%, most preferably in the amount of about 0.2 to 0.3 vol%.
Antifoamants such as silicone antifoaming agents can be present in the amount of about 0.001 to 0.2 vol%, more preferably in the amount of about 0.005 to 0.15 vol%, most preferably in the amount of about 0.01 to 0.1 vol%.
Lubricating oil additives are described generally in" Lubricants and Related Products" by Dieter Klamann, Verlag Chemie, Deerfield, Florida, 1984,and also in" Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith, 1967, page 1- 11, the disclosures of which are incorporated herein by reference.
The present invention is illustrated further in the following nonlimiting examples and comparative examples.
EXPERIMENTAL
Lab Nitration Screener Test Results A lab nitration screener test was used in initial experiments to guide in the 20 selection of detergents, antioxidants, and viscosity index improvers (VIs).
The test results identify a number of parameters for assessing the used oil performance, including viscosity increase, oxidation, and nitration. All measurements are reported on a relative basis so that large results or values represent go* WO 01/44418 PCT/US00/33683 greater levels of lubricant degradation. Thus, numerically lower results represent a measure of longer oil life. In each test, a Reference Oil is always tested. All results are reported as a ratio of the result for the oil tested divided by the result for a Reference Oil. For example, if a tested oil has an oxidation result of 1.0, then it has an oxidation performance equal to that of the Reference Oil. If the tested oil has an oxidation result less than 1.0, then the tested oil demonstrates oxidation performance superior to that of the Reference Oil.
Examples Lab nitration screener test results are summarized in Table 1.
Results are measured relative to Reference Oil B, which is a commercial medium ash gas engine oil based on solvent-extracted basestocks. Reference Oil B is the most widely .old aedium ash gas .engine oil in Cana nd therefore represents a "benchmark standard" against which other formulations useful as engine oils may be measured. Comparative Oil 1 is another commercial medium ash gas engine oil, formulated with Oloa 1255 additive package in solventextracted basestocks. Oloa 1255 is one of the most widely sold gas engine oil additive packages and therefore Comparative Oil 1 represents another "benchmark standard" against which other formulations may be measured. Comparative Oil 2 is a medium ash formulation blended using a combination of low TBN calcium sulphonate, medium TBN calcium phenate and high TBN calcium phenate.
Results show that the oil of the present invention, Example 1, demonstrates superior performance to those of the Comparative oils, in terms of reduced oxidation, nitration and viscosity increase, and superior performance to that of Reference Oil B in terms of reduced oxidation and nitration and equal to Reference Oil B for reduced viscosity increase. Example 1 contains a mixture of WO 01/44418 PCT/US00/33683 -16three metal salt detergents, one each from the group high TBN, medium TBN and low/neutral TBN detergents, wherein at least one metal salicylate is used as the medium or low/neutral salt detergent. The invention provided performance superior to that of the other oils that used different detergents or mixtures of detergents.
0 0 TABLE I 00 TEST FORMULATIONS AND NITRATION TEST RESULTS Component Reference Comparative Comparative Reference Example (VI/)Description Oil 13 Oil I Oil 2 Oil B* _______Commercial oil l00'.00 100.0 _______Commercial oil 100.00 SN base oil 86.70 _1200 SIN base oil 2.68 SN base oil 4.35 SN base oil 86.20 TBN Ca phenate detergent 2.47 Ca sulphonate (26 TBN) 0.81 0.81 _______Dispersant 4.00 Metal deactivator -0.05 ZDDP _______Antifoamant 0.05 point depressant 0.40 _______Antioxidant 1.00 of additive system 5.79 Ca alkylsalicylate (64 TBN) 2.00 ________Overbased Ca phenate (190 TBN) 1.55-- _________Overbased Ca sulphonate (300 TBN) 08 ~wa: -~1 7 cj~ 0 0 0 TABLE 1 (continued) TEST FORMULATIONS AND NITRATION TEST RESULTS Component Reference Comparative Comparative Reference Example (Vol%) Description OilB oil I Oil 2 Oil B* 1 viscosity measured kV 100*C 13.55 13.53 13.54 13.46 13.19 Nirto etoxidation (relative) 1.00 1.11 0.90 1.00 0.62 nitration (relative) 1.00) 1.04 1.16 1.00 0.77 viscosity increase (relative) 1.00 1.62 1.24 1.00 1.00 Total medium low TBN detergents vol%, by ai. IN/A 1.47 N/A 1.36 high TBN detergents voI%, by a.i. IN/A 0.62 N/A 0.47 medium low TBN detergents ratio, vol% N/A 0.42 N/A 0.35 Notes: B* is a repeat blend of B using sarjac components and exact same formulafion.
Claims (8)
19- CLAIMS: 1. A long life lubricant comprising a major amount of an oil of lubricating viscosity and a minor amount of additives comprising a mixture of detergents comprising a first metal salt or group of metal salts selected from the group consisting of one or more metal salicylate(s), metal sulfonate(s), metal phenate(s), and mixtures thereof having a high Total Base Number (TBN) of greater than about 150 or higher used in an amount in combination with the other metal salts or groups of metal salts sufficient to achieve a lubricating oil of at least 0.65 wt%/ sulfated ash content, a second metal salt or group of metal salts selected from the group consisting of one or more metal salicylate(s) metal sulfonate(s), metal phenate(s) and mixture thereof having a medium TBN of greater than about 50 to 150, and a third metal salt or group of metal salts selected from the group consisting of one or more metal sulfonate(s), metal iulty laIes) iuu 1111ALL C3 U1CI CV1 Iiglljr a IV WI1 &UU€1A I A 1 N WU AV tv the total amount of medium plus low/neutral TBN detergents being about 0.7 vol% or higher (based on active ingredient), the total amount of high TBN detergents being about 0.3 vol% or higher (based on active ingredient) and the volume ratio (based on active ingredient) of high TBN detergent to medium plus low/neutral TBN detergent is in the range of about 0.15 to 3.5, wherein at least one of the medium or low/neutral TBN detergent(s) is metal salicylate. 2. The long life lubricant composition of claim I wherein the at least one of the medium TBN detergent(s) is a metal salicylate. 3. The long life lubricant composition of claim 1 wherein the metal components of the metal sulfonate, metal phenate and metal salicylate are the same or different and are selected from the group consisting of alkali metals and alkaline earth metals. WO001/44418 PCT/US00/33683 20 4. The long life lubricant composition of claim I wherein the total amount of the metal salicylate(s) in the mixture is in the amount of 0.5 to vol% based on active ingredient. The long life lubricant composition of claim 4 wherein the mixture of detergents is present in an amount up to about 10 vol% based on active ingredients. 6. The long life lubricant of claim I wherein the total amount of medium plus low/neutral TBN detergent is about 0.9 vol% or higher, based on active ingredient. medium plus low/neutral TBN detergent is about 1 vol% or higher, based on active ingredient. 8. The long life lubricant of claim 1, 2, 3, 4, 5, 6 or 7 wherein the total amount of high TBN detergent is about 0.4 vol% or higher, based on active ingredient. 9. The long life lubricant of claim 1, 2, 3, 4, 5, 6 or 7 wherein the total amount of high TBN detergent is about 0.5 vol% or higher, based on active ingredient. The long life lubricant composition of claim 1, 2, 3, 4, 5, 6 or 7 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.2 to 2. 11. The long life lubricant composition of claim 1, 2, 3, 4, 5, 6 or 7 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.25 to 1. 12. The long life lubricant composition of claim 8 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.2 to 2. 13. The long life lubricant composition of claim 8 wherein the volume or ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.25 to 1. 14. The lubricant composition of claim 1 wherein the first salt has a TBN of nreater than ahout 1 50 to 300. A method for enhancing the life of a lubricating oil composition as evidenced by a reduction in viscosity increase, oxidation and nitration by adding to the oil a minor amount of additives comprising a mixture of detergents comprising a first metal salt or group of metal salts selected from the group consisting of one or more metal salicylate(s), metal sulfonate(s), metal Sphenate(s), and mixtures thereof having a high Total Base Number (TBN) of greater than about 150 or higher used in an amount in combination with the other metal salts or groups of metal salts sufficient to achieve a lubricating oil of at least 0.65 wt% sulfated ash content, a second metal salt or group of metal salts selected from the group consisting of one or more metal salicylate(s), metal sulfonate(s), metal phenate(s), and mixture thereof having a medium TBN of greater than about 50 to 150, and a third metal salt or group of metal salts selected from the group consisting of one or more metal sulfonate(s), metal salicylate(s) and mixtures thereof having a low/neutral TBN of about 10 to 50, the total amount of medium plus low/neutral TBN detergents being about 0.7 vol% or higher (based on active ingredient), the total amount of high TBN detergents being about 0.3 vol% or higher (based on active ingredient) and the volume ratio (based on active ingredient) of high TBN detergent to medium plus low/neutral TBN detergent is in the range of about 0.15 to 3.5, wherein at least one of the medium or low/neutral TBN detergent(s) is metal salicylate. 16. The method of claim 15 wherein the at least one of the medium TBN detergent(s) is a metal salicylate. 17. The method of claim 15 wherein the metal components of the metal sulfonate, metal phenate and metal salicylate are the same or different and are selected from the group consisting of alkali metals and alkaline earth metals. 18. The method of claim 15 wherein the total amount of the metal salicylate(s) in the mixture is in the amount of 0.5 to 4.5 vol% based on active ingredient. 19. The method of claim 15 wherein the mixture of detergents is present in an amount up to about 10 vo!% based on active innredients. The method of claim 15 wherein the total amount of medium plus low/neutral TBN detergent is about 0.9 vol% or higher, based on active ingredient.
21. The method of claim 15 wherein the total amount of medium plus low/neutral TBN detergent is about 1 vol% or higher, based on active ingredient.
22. The method of claim 15, 16, 17, 18, 19, 20 or 21 wherein the total amount of high TBN detergent is about 0.4 vol% or higher, based on active ingredient.
23. The method of claim 15, 16, 17, 18, 19, 20 or 21 wherein the total amount of high TBN detergent is about 0.5 vol% or higher, based on active ingredient.
24. The method of claim 15, 16, 17, 18, 19, 20 or 21 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.2 to 2. The method of claim 15, 16, 17, 18, 19, 20 or 21 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.25 to 1.
26. The method of claim 22 wherein the volume ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.2 to 2.
27. The method of claim 23 wherein the volume or ratio, based on active ingredient, of the high TBN detergent to the medium plus low/neutral TBN detergent is in the range of about 0.25 to 1.
28. The method of claim 15 wherein the first metal salt has a TBN of greater than about 150 to 300. DATED this 17 th day of August 2004 EXXONMOBIL RESEARCH AND ENGINEERIGN COMPANY WATERMARK PATENT TRADE MARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA P21357AU00 0* o S S 0 S
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US09/464,530 US6191081B1 (en) | 1999-12-15 | 1999-12-15 | Long life medium and high ash oils with enhanced nitration resistance |
US09/464530 | 1999-12-15 | ||
PCT/US2000/033683 WO2001044418A1 (en) | 1999-12-15 | 2000-12-13 | Long life medium and high ash oils with enhanced nitration resistance |
Publications (2)
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AU2091201A AU2091201A (en) | 2001-06-25 |
AU777654B2 true AU777654B2 (en) | 2004-10-28 |
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AU20912/01A Ceased AU777654B2 (en) | 1999-12-15 | 2000-12-13 | Long life medium and high ash oils with enhanced nitration resistance |
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US (1) | US6191081B1 (en) |
EP (1) | EP1250407B1 (en) |
JP (1) | JP2003517093A (en) |
AT (1) | ATE320477T1 (en) |
AU (1) | AU777654B2 (en) |
CA (1) | CA2393138C (en) |
DE (1) | DE60026735T2 (en) |
DK (1) | DK1250407T3 (en) |
NO (1) | NO20022843L (en) |
WO (1) | WO2001044418A1 (en) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7166562B2 (en) * | 1998-10-13 | 2007-01-23 | Exxonmobil Research And Engineering Company | Long life gas engine oil and additive system |
EP1195425A1 (en) * | 2000-10-05 | 2002-04-10 | Infineum International Limited | Lubricating oil composition for gas-fuelled engines |
EP1304368A1 (en) * | 2001-09-28 | 2003-04-23 | Infineum International Limited | A gas engine lubricating oil composition |
US6756348B2 (en) | 2001-11-29 | 2004-06-29 | Chevron Oronite Company Llc | Lubricating oil having enhanced resistance to oxidation, nitration and viscosity increase |
US6642191B2 (en) | 2001-11-29 | 2003-11-04 | Chevron Oronite Company Llc | Lubricating oil additive system particularly useful for natural gas fueled engines |
US20030171228A1 (en) * | 2002-01-31 | 2003-09-11 | Deckman Douglas Edward | Mixed TBN detergents and lubricating oil compositions containing such detergents |
US20030191032A1 (en) * | 2002-01-31 | 2003-10-09 | Deckman Douglas E. | Mixed TBN detergents and lubricating oil compositions containing such detergents |
EP1347033A1 (en) * | 2002-03-12 | 2003-09-24 | Infineum International Limited | A gas engine lubricating oil composition |
US7087557B2 (en) * | 2002-07-23 | 2006-08-08 | Crompton Co./Cie | Metal-containing neutral and overbased salicylates based on styrenated salicylic acid |
US7183241B2 (en) * | 2002-10-15 | 2007-02-27 | Exxonmobil Research And Engineering Company | Long life lubricating oil composition with very low phosphorus content |
US20050153851A1 (en) * | 2002-10-18 | 2005-07-14 | Cartwright Stanley J. | Long life lubricating oil with enhanced oxidation and nitration resistance |
CN100513539C (en) * | 2003-02-20 | 2009-07-15 | 中国石油天然气股份有限公司 | Low ash gas engine lubricating oil composition |
US20040220059A1 (en) * | 2003-05-01 | 2004-11-04 | Esche Carl K. | Low sulfur, low ash, low and phosphorus lubricant additive package using overbased calcium oleate |
US20040224858A1 (en) * | 2003-05-06 | 2004-11-11 | Ethyl Corporation | Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate |
US20040241309A1 (en) * | 2003-05-30 | 2004-12-02 | Renewable Lubricants. | Food-grade-lubricant |
AU2004273094B2 (en) * | 2003-09-12 | 2008-07-10 | Renewable Lubricants, Inc. | Vegetable oil lubricant comprising all-hydroprocessed synthetic oils |
US20060211585A1 (en) * | 2003-09-12 | 2006-09-21 | Renewable Lubricants, Inc. | Vegetable oil lubricant comprising Fischer Tropsch synthetic oils |
US7585822B2 (en) * | 2004-11-23 | 2009-09-08 | Crompton Corporation | Emulsifier blends for lubricating oils |
CA2609652C (en) * | 2005-04-26 | 2013-09-10 | Renewable Lubricants, Inc. | High temperature biobased lubricant compositions comprising boron nitride |
EP1721958A1 (en) * | 2005-05-10 | 2006-11-15 | Infineum International Limited | Detergent |
US20070117726A1 (en) * | 2005-11-18 | 2007-05-24 | Cartwright Stanley J | Enhanced deposit control for lubricating oils used under sustained high load conditions |
US8680030B2 (en) * | 2005-11-18 | 2014-03-25 | Exxonmobil Research And Engineering Company | Enhanced deposit control for lubricating oils used under sustained high load conditions employing glycerine derivative with a grafted hindered phenolic and/or a hindered phenolic containing a thioether group |
EP2148915A1 (en) * | 2007-04-24 | 2010-02-03 | ExxonMobil Research and Engineering Company | Long-life engine oil composition with low or no zinc content |
US8383563B2 (en) * | 2007-08-10 | 2013-02-26 | Exxonmobil Research And Engineering Company | Method for enhancing the oxidation and nitration resistance of natural gas engine oil compositions and such compositions |
EP2048218A1 (en) * | 2007-10-09 | 2009-04-15 | Infineum International Limited | A lubricating oil composition |
WO2010009036A2 (en) * | 2008-07-16 | 2010-01-21 | The Lubrizol Corporation | Improved lubricant for natural gas engines |
US8642523B2 (en) | 2010-02-01 | 2014-02-04 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
US8598103B2 (en) | 2010-02-01 | 2013-12-03 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient |
US8728999B2 (en) | 2010-02-01 | 2014-05-20 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
SG182504A1 (en) | 2010-02-01 | 2012-08-30 | Exxonmobil Res & Eng Co | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
US8759267B2 (en) | 2010-02-01 | 2014-06-24 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
US8748362B2 (en) | 2010-02-01 | 2014-06-10 | Exxonmobile Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient |
CA2863895C (en) * | 2013-09-23 | 2021-11-09 | Chevron Japan Ltd. | A fuel economy engine oil composition |
US10364403B2 (en) | 2013-11-06 | 2019-07-30 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
SG11201603378WA (en) | 2013-11-06 | 2016-05-30 | Chevron Oronite Technology Bv | Marine diesel cylinder lubricant oil compositions |
KR20230062403A (en) * | 2021-10-29 | 2023-05-09 | 인피늄 인터내셔날 리미티드 | Method of limiting chemical degradation due to nitrogen dioxide contamination |
CA3180270A1 (en) | 2021-10-29 | 2023-04-29 | Infineum International Limited | Ionic liquid composition |
US12006486B2 (en) | 2021-10-29 | 2024-06-11 | Infineum International Limited | Method of limiting chemical degradation due to nitrogen dioxide contamination |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US571907A (en) * | 1896-11-24 | Charles e | ||
US5328620A (en) * | 1992-12-21 | 1994-07-12 | The Lubrizol Corporation | Oil additive package useful in diesel engine and transmission lubricants |
US5792735A (en) * | 1994-01-11 | 1998-08-11 | Bp Chemicals (Additives) Limited | Lubricating oil compositions |
Family Cites Families (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3256183A (en) | 1963-07-10 | 1966-06-14 | Lubrizol Corp | Lubricant having improved oxidation resistance |
GB1404660A (en) | 1971-11-26 | 1975-09-03 | Standard Oil Co | Five-grade motor oil for internal combustion engines |
US4171269A (en) | 1976-12-27 | 1979-10-16 | Texaco Inc. | Sulfurized lubricant composition |
US5262073A (en) | 1978-08-30 | 1993-11-16 | Mobil Oil Corporation | Lubricant composition |
US4181619A (en) | 1978-10-30 | 1980-01-01 | Mobil Oil Corporation | Antiwear composition |
CA1136606A (en) | 1978-12-11 | 1982-11-30 | Timothy R. Erdman | Fuel economy in internal combustion engines |
AU549639B2 (en) | 1981-07-01 | 1986-02-06 | Chevron Research Company | Lubricating oil composition to improve fuel economy |
AU550869B2 (en) | 1981-08-03 | 1986-04-10 | Chevron Research Company | Lubricating oil with borated long chain 1,2 alkane diol friction modifier |
US4375418A (en) | 1981-10-28 | 1983-03-01 | Texaco Inc. | Lubricating oil composition |
US4925579A (en) | 1983-06-20 | 1990-05-15 | Chevron Research Company | Lubricating oil containing hydroperoxidized ethylene copolymers and terpolymers as dispersants and V.I. improvers |
JPS606790A (en) | 1983-06-27 | 1985-01-14 | Idemitsu Kosan Co Ltd | Lubricating oil composition for diesel engine |
US4764296A (en) | 1986-02-28 | 1988-08-16 | Amoco Corporation | Railway lubricating oil |
US4792410A (en) | 1986-12-22 | 1988-12-20 | The Lubrizol Corporation | Lubricant composition suitable for manual transmission fluids |
US4784781A (en) | 1987-02-27 | 1988-11-15 | The Lubrizol Corporation | Lubricating oil compositions containing multi-functional additive component |
CA1337294C (en) | 1987-11-20 | 1995-10-10 | Dale Robert Carroll | Lubricant compositions for enhanced fuel economy |
CA1337293C (en) | 1987-11-20 | 1995-10-10 | Emil Joseph Meny | Lubricant compositions for low-temperature internal combustion engines |
US5202036A (en) | 1990-06-28 | 1993-04-13 | The Lubrizol Corporation | Diesel lubricants and methods |
JPH05331481A (en) | 1992-05-29 | 1993-12-14 | Tonen Corp | Lubricant composition for two-cycle engine |
US5320763A (en) | 1993-03-12 | 1994-06-14 | Chevron Research And Technology Company | Low viscosity group II metal overbased sulfurized C10 to C16 alkylphenate compositions |
US5318710A (en) | 1993-03-12 | 1994-06-07 | Chevron Research And Technology Company | Low viscosity Group II metal overbased sulfurized C16 to C22 alkylphenate compositions |
GB9305417D0 (en) | 1993-03-16 | 1993-05-05 | Ethyl Petroleum Additives Ltd | Gear oil lubricants of enhanced friction properties |
JP3613530B2 (en) | 1993-05-27 | 2005-01-26 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
JP2624122B2 (en) | 1993-06-15 | 1997-06-25 | 住友金属工業株式会社 | Lubricant composition for hot rolling |
US5691283A (en) * | 1994-03-01 | 1997-11-25 | Ethyl Petroleum Additives Limited | Use of transmission and gear oil lubricants having enhanced friction properties |
JPH07247494A (en) | 1994-03-11 | 1995-09-26 | Cosmo Sogo Kenkyusho:Kk | Reclaimed lubricant composition |
JPH07316577A (en) | 1994-05-20 | 1995-12-05 | Tonen Corp | Lubricant oil composition |
GB9413976D0 (en) | 1994-07-11 | 1994-08-31 | Exxon Chemical Patents Inc | Multigrade lubricating compositions |
CA2207676A1 (en) | 1994-12-20 | 1996-06-27 | Elisavet P. Vrahopoulou | Engine oil with improved fuel economy properties |
JP3168267B2 (en) | 1994-12-27 | 2001-05-21 | 株式会社コスモ総合研究所 | Diesel engine oil composition |
JPH08253782A (en) | 1995-03-14 | 1996-10-01 | Idemitsu Kosan Co Ltd | Lubricating oil composition for internal combustion engine |
JP3450934B2 (en) | 1995-04-18 | 2003-09-29 | 株式会社コスモ総合研究所 | Engine oil composition |
US5744430A (en) * | 1995-04-28 | 1998-04-28 | Nippon Oil Co., Ltd. | Engine oil composition |
US5726133A (en) | 1996-02-27 | 1998-03-10 | Exxon Research And Engineering Company | Low ash natural gas engine oil and additive system |
US5719107A (en) * | 1996-08-09 | 1998-02-17 | Exxon Chemical Patents Inc | Crankcase lubricant for heavy duty diesel oil |
JP3241603B2 (en) | 1996-08-09 | 2001-12-25 | 株式会社ジャパンエナジー | Lubricating oil for diesel engines |
JP4028614B2 (en) * | 1997-02-03 | 2007-12-26 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
JP4813633B2 (en) | 1997-04-16 | 2011-11-09 | 出光興産株式会社 | Diesel engine oil composition |
US5804537A (en) * | 1997-11-21 | 1998-09-08 | Exxon Chemical Patents, Inc. | Crankcase lubricant compositions and method of improving engine deposit performance |
CN1105165C (en) * | 1997-11-28 | 2003-04-09 | 英菲诺姆美国公司 | Lubricating oil compositions |
US5906969A (en) | 1998-05-01 | 1999-05-25 | Exxon Research And Engineering Company | High fuel economy passenger car engine oil |
JP5057603B2 (en) * | 1998-05-01 | 2012-10-24 | 昭和シェル石油株式会社 | Lubricating oil composition for internal combustion engines |
JP2001158896A (en) * | 1999-12-02 | 2001-06-12 | Chevron Oronite Ltd | Lubricant oil composition for internal combustion engine especially effective for lubricant of gas engine |
-
1999
- 1999-12-15 US US09/464,530 patent/US6191081B1/en not_active Expired - Lifetime
-
2000
- 2000-12-13 AT AT00984262T patent/ATE320477T1/en not_active IP Right Cessation
- 2000-12-13 CA CA002393138A patent/CA2393138C/en not_active Expired - Fee Related
- 2000-12-13 AU AU20912/01A patent/AU777654B2/en not_active Ceased
- 2000-12-13 DK DK00984262T patent/DK1250407T3/en active
- 2000-12-13 DE DE60026735T patent/DE60026735T2/en not_active Expired - Fee Related
- 2000-12-13 WO PCT/US2000/033683 patent/WO2001044418A1/en active IP Right Grant
- 2000-12-13 JP JP2001545496A patent/JP2003517093A/en active Pending
- 2000-12-13 EP EP00984262A patent/EP1250407B1/en not_active Expired - Lifetime
-
2002
- 2002-06-14 NO NO20022843A patent/NO20022843L/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US571907A (en) * | 1896-11-24 | Charles e | ||
US5328620A (en) * | 1992-12-21 | 1994-07-12 | The Lubrizol Corporation | Oil additive package useful in diesel engine and transmission lubricants |
US5792735A (en) * | 1994-01-11 | 1998-08-11 | Bp Chemicals (Additives) Limited | Lubricating oil compositions |
Also Published As
Publication number | Publication date |
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DE60026735D1 (en) | 2006-05-11 |
NO20022843D0 (en) | 2002-06-14 |
DE60026735T2 (en) | 2006-11-16 |
EP1250407B1 (en) | 2006-03-15 |
ATE320477T1 (en) | 2006-04-15 |
EP1250407A1 (en) | 2002-10-23 |
CA2393138A1 (en) | 2001-06-21 |
EP1250407A4 (en) | 2003-07-16 |
NO20022843L (en) | 2002-07-02 |
US6191081B1 (en) | 2001-02-20 |
AU2091201A (en) | 2001-06-25 |
JP2003517093A (en) | 2003-05-20 |
DK1250407T3 (en) | 2006-07-10 |
WO2001044418A1 (en) | 2001-06-21 |
CA2393138C (en) | 2010-01-05 |
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